N-tetrahaloethylthio pyrazole pesticides



United States Patent O 3,409,632 N -TETRAHALOETHYLTHIO PYRAZOLE PESTICIDES Oakland, Calif assignor to Chevron Joseph G. E. Feuyes,

San Francisco, Calif., a corporation Research Company, of Delaware Drawing. Continuation-impart of application Ser. No. 573,878, Aug. 22, 1966. This application June 5, 1967, Ser. No. 643,415

7 Claims. (Cl. 260-310) ABSTRACT OF THE DISCLOSURE N-(1,1,2,2-tetrahaloethylthio) pyrazoles in which the pyrazole nucleus is substituted in the 3 and positions with hydrogen or lower alkyl groups and in the 4 position with hydrogen, halogen or a nitro group. Compounds of this class are fungicidal and bactericidal. They are made by reacting a pyrazole or its alkali metal salt with tetrahaloethylsulfenyl halides.

CROSS REFERENCE TO RELATED APPLICATION a continuation-in-part of copending 573,878, filed Aug. 22, 1966, now

This application is application Ser. No.

abandoned.

FIELD OF INVENTION This invention is directed to novel N-tetrahaloethylthio pyrazoles which are useful as pesticides. More particularly, it concerns N-(1,1,2,2-tetrahaloethylthio)-pyrazoles and their use as bactericides and fungicides.

INVENTION DESCRIPTION These unique compounds are N-tetrahaloethylthio pyrazoles in which the pyrazole nucleus is substituted in the 3 and 5 positions with hydrogen or alkyl groups having 1 to 4 carbon atoms and in the 4 position with hydrogen, halogen of atomic numbers 17 to 35, i.e., chlorine or bromine or a nitro group. These pyrazoles may be represented by the general formula where X is halogen of atomic numbers 17 to 35, R and R are individually hydrogen or alkyl of 1 to 4 carbon atoms and R is hydrogen, halogen of atomic numbers 17 to 35 or a nitro group. Preferably, R R and R are hydrogen and X is chlorine. A preferred alkyl group for R and R is methyl.

Specific examples of these novel compounds are:

N-(1,1,2',2'-tetrachloroethylthio)-pyrazole, N-(1',1',2,2'-tetrabromoethylthio)-pyrazole, N-(2',2-di'bromo-1',1'-dichloroethylthio)-pyrazole, N-(1',1,2',2-tetrachloroethylthio)-4-chloropyrazole, N-l,1,2,2-tetrachloroethylthio) -3-methylpyrazole, N- 1 1 ',2,2-tetrachloroethylthi0) -3,5-dimethylpyrazole, N-( 1',2-di'bromo-1',2'-dichloroethylthio) -4-brornopyrazole,

3,409,632 Patented 0v. 5, 1968 N- l l ',2',2-tetrachloroethylthio -3-propylpyrazole,

N-l',1',2',2-tetrachloroethylthio)-5-butylpyrazole and N 1',1',2',2'-tetrachloroethylthio)-5-methyl-4-nitropyrazole.

The N-(1,1,2,2-tetrahaloethylthio) pyrazoles of this i prepared by reacting 1,1,2,2-tetrahalo- EXAMPLES The following examples illustrate specific methods by which compounds of this invention may be prepared. Unless otherwise indicated, percentages are by weight.

Example 1 Compound Percent Chlorine methylpyraz e 50. 65 52. 64 11. 45 12. 27 N-(1 ,1,2,2-tetrachloroethylthio)-3 nltropyrazole 45. 6 45. 5 10. 3 10. 0 N-(1,1,2,2-tetrachloroethylthio)-3- methyH-nitropyrazole 43. 63 43. 42 9. 86 9. 5 N-(1,l,2,2-tetrachloroethylthio)-4- bromopyrazole 14.49 "14. 49 9. 29 9. 12 N-(l,1Q2,2-tetrachloroethylthio)-3- methyl-4-bromopyraz0le *13. 92 14. 01 8. 93 8. 9

N-( l,1,2,2-tetrachloroethylthiolllidimethyl-i-bromopyrazole 13.4 '12. 87 8.69 8.34

*Halogen analysis in meq./g.

The pyrazoles, especially the unsubstituted and nitrosubstituted ing N-(polyhaloalkylthio)-pyrazoles, such as the N-(trihalomethylthio)-pyrazoles, as regards bactericidal activity. In tests against bacterial plant pathogens from such Cale. Found Cale. Found N- (1,1,2,2-tetachloroethylthio) -3- genera as Erwinia, Agrobacteria, Corynebacteria, XanfllOHtOHdS and Pseudomonas the compounds of this invention had ED s (effective dosage for 50% inhibition) as low as 0.5 p.p.m.

This bactericidal activity is illustrated by the data in Table II. The method used to develop these data was as follows: Bacteria suspensions were prepared by washing a culture of the desired bacteria from an agar slant with sterile water into a vessel and further diluting the aqueous suspension to 250 ml. with sterile water.

The pyrazole to be tested was dissolved in acetone to 500 p.p.m. and 30x of this solution was pipetted onto each of two surface areas on a plate covered with 20 ml. of Emersons agar. The treated agar plates were then sprayed with the bacteria suspension and the plates were incubated for 44 to 48 hours at 24 C. The two treated areas of the plate were then observed for bacterial growth. The pyrazoles effectiveness for controlling bacterial growth in the treated areas was rated as or indicating the areas were completely free of bacterial growth and indicating they were completely overgrown.

For comparison, N-(trichloromethylthio) pyrazole was also tested by this method.

TABLE II Effectiveness Compound E. caratovora P. syringae N-(1,1,2,2-tetraehloro ethylthio) pyrazola N-(l', 1, 2, 2tetrachloroethylthio)-3- pyrazole COMPARISON COMPOUND N-(trichloromethylthio) pyrazole The pyrazoles of this invention also exhibit excellent fungicidal activity. They are remarkably and surprisingly superior to corresponding N-(trichlorornethylthio) pyrazoles. The preferred compound of this invention, N-(l,1, 2,2 tetrachloroethylthio) pyrazole, is also effective in fungicidal applications in which the present commercial fungicide which contains an N-tetrachloroethylthio group is relatively ineffective. For instance, it may be applied as a vapor to stored grain, such as green corn, to control fungus diseases which attack the grain.

The fungicidal superiority of N-(l,l,2,2-tetrahaloethylthio) pyrazoles over corresponding N-(trichloromethylthio) pyrazoles was illustrated by testing N (l,l,2,2- tetrachloroethylthio) pyrazole and N- (trichloromethylthio) pyrazole under identical conditions by the following methods.

Mycelial Drop Method.-This test measures the fungitoxicity of a compound in terms of its inhibition of fungus mycelial growth. Each pyrazole was dissolved in acetone to a 125 p.p.m. concentration. Equal volumes of this solution were applied to the centers of each of three replicate paper discs inoculated with the desired fungus mycelium and placed on potato-dextrose agar medium. Following this application the discs were incubated along with inoculated but untreated control discs at ambient temperatures until the control discs were filled with mycelial growth. The fungicidal activity of the pyrazole was determined by comparing the radii of mycelial growth away from the edges of the treated and control discs. From this comparison a percent inhibition based on the relative mycelial growth areas was determined.

Slide Spore Germination Method.-This method is described in the American Phytopathological Society Journal, vol. 33, pages 627-632 (1943). It measures the fungitoxicity of compounds in terms of their percent inhibition of fungus spores. The general procedure was as follows: Each pyrazole to be tested was dissolved in acetone to a concentration of p.p.m. These solutions were then pipetted into the wells of depression slides and allowed to hosts such as plants,

dry. The wells were filled with a spore suspension of the specified test organism and incubated in a moist chamber overnight. A group of 100 spores was examined and the number of spores germinated and not germinated was counted and recorded to show the biological activity in terms of the percentage inhibition.

The results of these comparative fungicidal tests appear in Table III.

TABLE III Percent Inhibition Compound Mycelial Drop Slide Spore r P H R M A N-(1,1,2,2-tetrachloroethylthio) pyrazole 100 97 100 N-(trichloromethylthio) pyrazole P=Pythium ultimum; H=Helminthosporium sativum; R=Rhizocton5a sobmi; M=M0nilinia fructicola; A=Altemaria solant.

Other pyrazoles of this invention were tested by the Mycelial Drop Method described above except that they were dissolved in acetone to a concentration of 500 p.p.m. The results of these tests appear 1n Table IV.

TABLE IV Percent Inhibition Compound P H F R N-(l ,l' ,2 ,2 -tetrachloroethylthio)-4- nitropyrazole 100 100 90 100 N-(l ,l ,2 ,2-tetrachloroethylthio)-3 methyl-knitropy'razole 100 100 98 100 N-(l ,1 ,2 ,2-tetrachloroethylthio)A bromopyrazole 100 97 100 N- (1 ,l ,2 ,2-tetrachloroethylthio) -3,5-

dimethyl i bromopyrazole 100 100 78 100 N-(1,1,2,2'-tetrachloroethylthio)-3- methyl-'i-bromopyrazole 100 94 100 N-(l ,l ,2 ,2-tctrachloroethylthio)3 5 dimcthylpyrazole 100 94 100 P=Pythium ultimum; H=Helminthosporium sativum; ozysporum; R=Rhiz0ct0nia solani.

In addition to the specific applications and formulations illustrated above, the pyrazoles of this invention may be formulated and applied in bactericidal or fungicidal amounts, as the case may be, by conventional art methods to bacteria, fungi or hosts, especially vegetative plant seeds, paper and the like, which are attacked by these pathogens. Accordingly, they may be used with inert liquid and solid carriers as powders, solutions and dispersions. Pesticidal formulations of these pyrazoles may also contain stabilizers, spreading agents, wetting agents, sticking agents, fillers, other compatible pesticides and the like.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

What I claim is:

1. A compound having the formula F= Fusarium d X r r in- 1 wherein X is chlorine. 2 wherein R R and R of claim 2 wherein R and R are 3,409,632 5 6 7. The compound of claim 2 wherein R2 is nitro. 2,844,628 7/1958 Kuhle et a1.

2,888,462 5/1959 Cannon. References Clfed 3,178,447 4/1965 Kohn 260309.5 UNITED STATES PATENTS 2,553,770 5/1951 Kittleson 260--309.5 5 HENRY JILESPWW Exammer- 2,553,775 5/1951 Hawley et al. 260-3095 NATALIE TROUSOF, Assistant Examiner. 

